WO2020255776A1 - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymer Download PDFInfo
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- WO2020255776A1 WO2020255776A1 PCT/JP2020/022522 JP2020022522W WO2020255776A1 WO 2020255776 A1 WO2020255776 A1 WO 2020255776A1 JP 2020022522 W JP2020022522 W JP 2020022522W WO 2020255776 A1 WO2020255776 A1 WO 2020255776A1
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- vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Definitions
- the present invention relates to a method for producing a vinyl chloride-based polymer in a polymer equipped with a reflux capacitor.
- the vinyl chloride polymer is produced by a suspension polymerization method in an aqueous medium and a water-soluble substance having surface activity (for example, partially saponified polyvinyl alcohol or cellulose ether) is used as the dispersant.
- a water-soluble substance having surface activity for example, partially saponified polyvinyl alcohol or cellulose ether
- heat is removed by a reflux condenser, the amount of heat removed increases, and as a result, it becomes difficult to obtain a polymer having a certain quality as desired, such as the particle size distribution, porosity, and bulk density of the vinyl chloride polymer. There was a problem that it would end up.
- An object of the present invention is to suppress foaming of the polymer slurry when polymerization is carried out using a polymer in the production of a vinyl chloride polymer, and to obtain a bulk specific gravity of the obtained vinyl chloride polymer. It is an object of the present invention to provide a method capable of producing a vinyl chloride polymer without adversely affecting the quality.
- a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith is polymerized in an aqueous medium using a polymer, and chloride is used.
- a method for producing a vinyl-based polymer in which an aqueous solution of a copolymer polyether having a weight average molecular weight of 1000 to 3500 and a molar ratio of ethylene oxide to propylene oxide of 10/90 to 60/40 is applied to the above-mentioned polymer.
- a method for producing a vinyl chloride-based polymer which comprises adding 0.005 parts by weight to 0.050 parts by weight as the copolymerized polyether with respect to 100 parts by weight of the charged vinyl chloride monomer. To do.
- the aqueous solution of the above copolymerized polyether at the polymerization step of the polymerization rate of 30% to 80%.
- the capacity of the above-mentioned polymerizer is 50 m 3 or more in volume.
- a reflux capacitor is attached.
- a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer is polymerized in an aqueous medium to produce a vinyl chloride polymer.
- the polymerization reaction solution does not substantially foam, and a vinyl chloride-based polymer having stable quality can be produced.
- the monomer raw material used in the present invention is a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer as a main component.
- the monomer mixture containing the vinyl chloride monomer as a main component contains at least 50% by weight or more, preferably 80% by weight or more of the vinyl chloride monomer and another simple copolymerizable with the vinyl chloride monomer. It is a mixture consisting of a monomer.
- Examples of other monomers copolymerizable with the vinyl chloride monomer used here include vinyl esters such as vinyl acetate and vinyl propionate; methyl (meth) acrylate, ethyl (meth) acrylate and the like.
- Examples thereof include (meth) acrylic acid esters; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; and monomers such as vinylidene chloride. These monomers may be used alone or in combination of two or more.
- the copolymerized polyether is a copolymer obtained by polymerizing ethylene oxide and propylene oxide in the above molar ratio, and has a structural unit derived from ethylene oxide and a structural unit derived from propylene oxide.
- the weight average molecular weight is measured by GPC in terms of styrene.
- the molecular weight is less than 1000, the action of lowering the interfacial tension of bubbles generated in the polymerization system and breaking the bubbles is reduced, so that the defoaming effect during polymerization is not sufficient and it is necessary to increase the amount used. There is a problem that it affects the quality of the obtained polymer. On the other hand, if it exceeds 3500, the copolymerized polyether is difficult to diffuse and the defoaming effect is lowered, particularly in a large polymer, and a vinyl chloride polymer having deteriorated quality is obtained.
- copolymerized polyether of ethylene oxide and propylene oxide may be a block copolymer or a random copolymer.
- the copolymerized polyether of ethylene oxide and propylene oxide is preferably used in an aqueous solution state, and is adjusted so that the solid content is 0.1 wt% to 50 wt%. At this time, ethanol or the like may be blended as an organic solvent if necessary. In other words, in the present invention, a solution of a copolymerized polyether containing an organic solvent may be used.
- the copolymerized polyether is added as an aqueous solution to the polymerization reaction system using 0.005 to 0.050 parts by weight, preferably 0.010 to 0.030 parts by weight, based on the charged vinyl chloride monomer.
- the amount of the copolymerized polyether used with respect to the charged vinyl chloride monomer is less than 0.005 parts by weight, the defoaming effect cannot be sufficiently produced.
- it exceeds 0.050 parts by weight not only the amount used increases, which is economically disadvantageous, but also scale tends to adhere to the wall surface of the polymer, which may increase fish eyes.
- the copolymerized polyether is added to the polymerization reaction system as an aqueous solution having a concentration of usually 0.1 to 50% by weight, preferably 0.5 to 20% by weight.
- the copolymerized polyether aqueous solution may be added when the polymerization rate is in the range of 30 to 80%, preferably 60 to 80%.
- the addition time is before the polymerization rate reaches 30%, the particle formation of the polymer is insufficient, and the addition may adversely affect the particle size distribution.
- the polymerization rate exceeds 80%, the foaming peak has already passed, so that the polymerization reaction solution may be blown up into the capacitor and the polymer particles may be deposited in the capacitor. , The effect of adding antifoaming agent becomes small.
- the aqueous medium examples include clean water, deionized water, distilled water, water such as ultrapure water, and a mixed medium of water and a water-soluble organic solvent.
- the water-soluble organic solvent examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and diethylene glycol.
- the content of the water-soluble organic solvent in the aqueous medium is preferably more than 0% by mass and 50% by mass or less.
- the dispersant usually used when polymerizing the above-mentioned vinyl chloride or a monomer mixture containing vinyl chloride in an aqueous medium is not particularly limited, and is used for producing a conventional vinyl chloride-based polymer. It doesn't matter.
- the dispersant include water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose; water-soluble partially saponified polyvinyl alcohols; acrylic acid polymers; water-soluble polymers such as gelatin; sorbitan monolaurate.
- Oil-soluble emulsifiers such as sorbitan triolate, glycerin tristearate, ethylene oxide-propylene oxide block copolymer; and water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, sodium laurate, etc. Be done. These may be used alone or in combination of two or more, and the amount used is preferably 0.010 to 0.200 parts by weight, more preferably 0.010 to 0.200 parts by mass, based on 100 parts by mass of the charged vinyl chloride monomer. It is preferably 0.030 to 0.15 parts by mass.
- the polymerization initiator which is usually used is not particularly limited, and may be one used in the production of a conventional vinyl chloride polymer.
- the polymerization initiator include peroxycarbonate compounds such as diisopropylperoxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, and diethoxyethylperoxydicarbonate; tert-butylperoxypivalate, tert-.
- Peroxy ester compounds such as hexyl peroxypivalate, tert-butyl peroxyneodecanate, ⁇ -cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxy Peroxides such as acetate, 3,5,5-trimethylhexanoyl peroxide; azo compounds such as azobis (2,4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile); Examples thereof include potassium sulfate; ammonium persulfate; and hydrogen peroxide.
- the amount used is preferably 0.010 to 0.200 parts by weight, more preferably 0.010 to 0.200 parts by mass, based on 100 parts by mass of the charged vinyl chloride monomer. It is preferably 0.03 to 0.15 parts by mass.
- the antioxidant which is usually used is not particularly limited, and may be one which is generally used for producing a vinyl chloride polymer.
- examples of this antioxidant include 2,2-bis (4-hydroxyphenyl) propane, hydroquinone, p-methoxyphenol, tert-butyl-hydroxyanisole, and n-octadecyl-3- (4-hydroxy-3,5).
- Phenol compounds such as semicarbazide, 1-acetylsemicarbazide, 1-chloroacetylsemicarbazide, 1-dichloroacetylsemicarbazide, 1-benzoylsemicarbazide, semicarbazone; derivatives of thiocarbazide such as carbohydrazide, thiosemicarbazide, thiosemicarbazide; Amin compounds such as N, N'-diphenyl-p-phenylenediamine, 4,4'-bis (2,4-dimethylbenzyl) diphenylamine; 4-nitroanisole, N-nitrosodiphenylamine, 4-nitroaniline, N-nitroso Nitro compounds or nitroso compounds such as phenylhydroxylylamine aluminum salts; triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphi
- 3,5-di-tert-butyl has good anti-initial colorability (property that coloring does not easily occur when the polymer is molded) and little scale adhesion to the polymer.
- -4-Hydroxytoluene triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], tert-butylhydroxyanisole, tert-butylhydroquinone, 2,6-di-
- tert-butyl-4-sec-butylphenol and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate may be used alone or in combination of two or more.
- the amount of these antioxidants used is preferably 0.050 parts by weight or less and 0 parts by mass or more with respect to 100 parts by mass of the charged vinyl chloride monomer.
- a degree of polymerization adjusting agent, a chain transfer agent, a gelation improving agent, an antistatic agent, etc. which are generally used for producing a vinyl chloride polymer, may be appropriately used.
- an antioxidant may be added to the polymerization system before the start of the polymerization, during the polymerization or at the end of the polymerization for the purpose of controlling the polymerization reaction and preventing the deterioration of the produced polymer.
- ⁇ Other conditions ⁇ Other conditions>
- other conditions in the polymerization for example, an aqueous medium in the polymerizer, a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer, a dispersion aid, a method of charging a polymerization initiator and the like, a charging ratio, and the like.
- the polymerization temperature and the like may be the same as the conventional conditions.
- the polymerizer is not particularly limited in shape, size, etc., and a durable polymerizer such as SUS may be generally used. From the viewpoint of productivity, the capacity is preferably 50 m 3 or more, more preferably 80 m. Polymerization may be carried out using three or more polymerizers, and in the case of the large-scale polymerizer, it is particularly preferable to provide a reflux capacitor in the polymerizer.
- the polymerization step is, for example, suspension polymerization.
- the vinyl chloride monomer or the vinyl chloride monomer mixture
- a jacket polymerizer
- the polymerization reaction is started by supplying warm water to the jacket.
- cold water is supplied to the jacket to keep the polymerization reaction temperature constant.
- the supply of cold water to the reflux condenser is started to carry out the polymerization.
- the polymerization conditions are not particularly limited, but for example, the vinyl-based monomer, other additives, suspending agents (water-soluble polymers such as cellulose and PVA) and aqueous components are placed in the polymerizer.
- the contents of the polymerizer are heated while stirring to carry out the polymerization reaction.
- the polymerization reaction is carried out at 20 to 80 ° C. for 1 to 20 hours.
- the stirring conditions may be adjusted as appropriate, but the polymerization is carried out while adjusting the rotation speed between 10 rpm and 300 rpm, preferably 50 and 200 rpm.
- the addition of the aqueous solution of the copolymerized polyether is carried out when the polymerization rate of vinyl chloride (or vinyl chloride monomer mixture) is 30% to 80%, preferably 60% to 80%, as described above. Good.
- the polymerization rate is the ratio of the obtained vinyl chloride resin (vinyl chloride-based polymer) to the total amount of the charged vinyl chloride monomer (or vinyl chloride monomer mixture).
- the polymerization rate is less than 30%, the polymerization may become unstable.
- the polymerization rate is 80% or more, the foam level has already passed the peak or has reached a level close to the peak, so that the effect may be reduced.
- the addition method is arbitrary, and it may be added all at once or gradually.
- Patent Document 1 has an excessively large weight average molecular weight of the defoaming agent, so that it is difficult to diffuse in the polymerizer and a sufficient defoaming effect is obtained. Not obtained.
- a copolymerized polyether having a specific weight average molecular weight is added in a specific amount at a specific polymerization step. Therefore, even in the case of a large-scale polymerizer or when a reflux capacitor is attached, the copolymerized polyether can be sufficiently diffused in the polymerizer, and a defoaming effect can be obtained. In addition, the quality of the obtained vinyl chloride polymer is not adversely affected.
- % described below means “% by weight”
- the polymerization rate is based on the result of performing polymerization in advance and determining the relationship between the polymerization time and the polymerization rate.
- the present invention was evaluated by dispersibility, defoaming property, and amount of PVC adhered to the wall surface.
- Example 1 In a stainless steel polymerizer with an internal volume of 100 m 3 equipped with a reflux condenser and a foam sensor, 49.0 tons of deionized water, 19.1 kg of partially saponified polyvinyl alcohol having a saponification degree of 80 mol%, and a methoxy substitution degree of 28.5 weight. % And 7.15 kg of hydroxymethyl cellulose having a hydroxylpropyl substituent of 8.9% by weight were charged, and then a predetermined amount of vinyl chloride monomer (35.0 tons) was charged. 17.5 kg of bis (2-ethylhexyl) peroxydicarbonate was charged as a polymerization initiator, and at the same time, warm water was passed through the jacket to start raising the temperature.
- a vinyl chloride polymer was obtained by adding 10 kg of 25% aqueous ammonia to the obtained polymer slurry to adjust the pH, and then dehydrating and drying the polymer slurry. In particular, there were no problems with particle size distribution, bulk specific gravity, and porosity.
- Example 2 Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 1,800 and a molar ratio of ethylene oxide to propylene oxide of 40/60 was used. There was.
- Example 3 Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,300 and a molar ratio of ethylene oxide to propylene oxide of 30/70 was used. There was.
- Example 4 Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 3,100 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
- Example 5 Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 1,100 and a molar ratio of ethylene oxide to propylene oxide of 10/90 was used. There was.
- Example 6 Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,800 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
- Example 7 Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,500 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
- Example 8 The procedure was the same as in Example 4 except that 175 kg of a 1% aqueous solution of the copolymerized polyether was added.
- Example 9 The procedure was the same as in Example 4 except that 1,050 kg of a 1% aqueous solution of the copolymerized polyether was added.
- Example 10 When the polymerization rate reached 40%, the same procedure as in Example 4 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
- Example 11 When the polymerization rate reached 80%, the same procedure as in Example 4 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
- Example 12 The procedure was the same as in Example 2 except that 175 kg of a 1% aqueous solution of the copolymerized polyether was added.
- Example 13 When the polymerization rate reached 40%, the same procedure as in Example 2 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
- Example 14 When the polymerization rate reached 80%, the same procedure as in Example 2 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
- Example 1 The procedure was the same as in Example 1 except that a stainless steel polymerizer having an internal volume of 100 m 3 equipped with a foam sensor was used without a reflux capacitor, and a polyether copolymer was not used. It was.
- Example 3 Experiments were carried out in the same manner as in Example 1 except that the following polyether copolymer was used, and the copolymer polyether having a weight average molecular weight of 1.5 million and a molar ratio of ethylene oxide to propylene oxide of 80/20 was used. A 1% aqueous solution was used.
- Example 4 Experiments were carried out in the same manner as in Example 1 except that the following polyether copolymer was used, and the copolymerized polyether having a weight average molecular weight of 15,000 and a molar ratio of ethylene oxide to propylene oxide of 20/80. A 1% aqueous solution of the above was used.
- a 1% aqueous solution of the copolymerized polyether was prepared, and the viscosity of the aqueous solution was measured with a digital rotational viscometer DV3T (manufactured by Eiko Seiki Co., Ltd.). The viscosity was measured at 20 ° C., and the viscosity measurement was performed at 250 rpm in Examples 1 to 10 and 100 rpm in Comparative Example 2. The viscosity of the 1% aqueous solution of the copolymerized polyether was evaluated as x, 1.5 cP or more and less than 10 cP as ⁇ , and less than 1.5 cP as ⁇ .
- ⁇ Evaluation of PVC adhesion to wall surface The amount of vinyl chloride resin adhering to the wall surface of the polymerization can was evaluated. The amount of vinyl chloride resin adhered per 1 cm 2 was visually evaluated as x for 100 grains or more, ⁇ for 10 grains or more and less than 100 grains, and ⁇ for less than 10 grains.
- ⁇ Plasticizer absorption amount Glass fiber was packed in the bottom of an aluminum alloy polymerizer having an inner diameter of 25 mm and a depth of 85 mm, 10 g of sample PVC was put into the polymerizer, and then 15 ml of dioctyl phthalate (DOP) was added. Then, after leaving it for 30 minutes to allow the sample to sufficiently permeate the DOP, an excess amount of DOP was centrifuged from the sample under an acceleration of 1500 G. The amount of DOP absorbed by the sample was determined as% by weight based on the weight of the sample before DOP absorption.
- DOP dioctyl phthalate
Abstract
This method for producing a vinyl chloride polymer involves using a polymerization device to polymerize a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer that is polymerizable therewith in an aqueous medium, wherein 0.005 parts by weight to 0.050 parts by weight of an aqueous solution of a copolymerized polyether having a weight-average molecular weight of 1000 to 3500 and a mole ratio of ethylene oxide and propylene oxide of 10/90 to 60/40 is added to the polymerization device with respect to 100 parts by weight of the vinyl chloride monomer loaded therein.
Description
本発明は、還流コンデンサーを付設した重合器中で塩化ビニル系重合体を製造する方法に関するものである。
The present invention relates to a method for producing a vinyl chloride-based polymer in a polymer equipped with a reflux capacitor.
近年、塩化ビニル系重合体の製造方法において、その生産性向上を目的として重合器の大型化と重合時間の短縮が進められてきている。重合時間短縮の手段として、重合器に還流コンデンサーを付設して重合反応熱の除熱を効率化し時間短縮する方法が用いられている。
In recent years, in the method for producing a vinyl chloride polymer, the size of the polymer and the shortening of the polymerization time have been promoted for the purpose of improving the productivity. As a means for shortening the polymerization time, a method is used in which a reflux capacitor is attached to the polymer to streamline the removal of heat of the polymerization reaction and shorten the time.
しかし、塩化ビニル系重合体の製造が、水性媒体中の懸濁重合法であって、かつ分散剤に界面活性を有する水溶性物質（例えば、部分鹸化ポリビニルアルコールやセルロースエーテル）を用いた場合には、還流コンデンサーによる除熱を行うと除熱量が増加し、それに伴い、塩化ビニル系重合体の粒度分布、ポロシティ、嵩密度等の目的とする一定の品質を有する重合体が得られにくくなってしまうという問題が生じていた。
However, when the vinyl chloride polymer is produced by a suspension polymerization method in an aqueous medium and a water-soluble substance having surface activity (for example, partially saponified polyvinyl alcohol or cellulose ether) is used as the dispersant. When heat is removed by a reflux condenser, the amount of heat removed increases, and as a result, it becomes difficult to obtain a polymer having a certain quality as desired, such as the particle size distribution, porosity, and bulk density of the vinyl chloride polymer. There was a problem that it would end up.
さらに発泡が激しくなると、重合反応液がコンデンサー内まで吹き上げて重合体粒子がコンデンサー内に堆積し、再度、反応液中に混入するなどするため、上記の問題に加えて、成形フィルム中のフィッシュアイや異物の増加といった重合体品質の悪化を引き起こすという問題があった。
When the foaming becomes more intense, the polymerization reaction solution is blown up into the capacitor, and the polymer particles are deposited in the capacitor and are mixed in the reaction solution again. Therefore, in addition to the above problems, the fish eye in the molded film. There was a problem of causing deterioration of polymer quality such as an increase in foreign matter and foreign matter.
このような還流コンデンサーによる除熱に伴う発泡を抑制する対策として、重量平均分子量が１５０万 ～２００万のエチレンオキシド／プロピレンオキシド共重合ポリエーテルを消泡剤として添加する方法が提案されている（特許文献１参照）。
As a measure to suppress foaming due to heat removal by such a reflux condenser, a method of adding an ethylene oxide / propylene oxide copolymerized polyether having a weight average molecular weight of 1.5 million to 2 million as a defoaming agent has been proposed (patented). Reference 1).
しかし、近年進められてきている大型化された重合器においては、この方法では消泡剤の重量平均分子量が大き過ぎるため、重合器中での拡散がしにくく十分な消泡効果が得られていない。
However, in the large-sized polymerizers that have been promoted in recent years, since the weight average molecular weight of the defoaming agent is too large by this method, it is difficult to diffuse in the polymerizer and a sufficient defoaming effect is obtained. Absent.
本発明の課題は、塩化ビニル系重合体の製造において、重合器を用いて重合を行った場合に、重合体スラリーの発泡を抑制し、かつ得られた塩化ビニル系重合体の嵩比重等の品質にも悪影響を与えることのない、塩化ビニル系重合体を製造できる方法を提供することである。
An object of the present invention is to suppress foaming of the polymer slurry when polymerization is carried out using a polymer in the production of a vinyl chloride polymer, and to obtain a bulk specific gravity of the obtained vinyl chloride polymer. It is an object of the present invention to provide a method capable of producing a vinyl chloride polymer without adversely affecting the quality.
上記課題を解決するために、本発明は、重合器を用いて、塩化ビニル単量体又は塩化ビニル単量体及びこれと共重合可能な単量体の混合物を水性媒体中で重合し、塩化ビニル系重合体を製造する方法であって、上記重合器に、重量平均分子量が１０００～３５００及びエチレンオキシドとプロピレンオキシドのモル比が１０／９０～６０／４０である共重合ポリエーテルの水溶液を、上記共重合ポリエーテルとして、仕込んだ上記塩化ビニル単量体１００重量部に対して０.００５重量部～０.０５０重量部添加することを特徴とする、塩化ビニル系重合体の製造方法を提供する。
In order to solve the above problems, in the present invention, a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith is polymerized in an aqueous medium using a polymer, and chloride is used. A method for producing a vinyl-based polymer, in which an aqueous solution of a copolymer polyether having a weight average molecular weight of 1000 to 3500 and a molar ratio of ethylene oxide to propylene oxide of 10/90 to 60/40 is applied to the above-mentioned polymer. Provided is a method for producing a vinyl chloride-based polymer, which comprises adding 0.005 parts by weight to 0.050 parts by weight as the copolymerized polyether with respect to 100 parts by weight of the charged vinyl chloride monomer. To do.
上記重合において、重合率３０％～８０％の重合段階で上記共重合ポリエーテルの水溶液を添加することが好ましい。
In the above polymerization, it is preferable to add the aqueous solution of the above copolymerized polyether at the polymerization step of the polymerization rate of 30% to 80%.
上記重合器の容量が容積５０ｍ3以上であることが好ましい。
上記重合器において、還流コンデンサーが付設されていることが好ましい。 It is preferable that the capacity of the above-mentioned polymerizer is 50 m 3 or more in volume.
In the above-mentioned polymerizer, it is preferable that a reflux capacitor is attached.
上記重合器において、還流コンデンサーが付設されていることが好ましい。 It is preferable that the capacity of the above-mentioned polymerizer is 50 m 3 or more in volume.
In the above-mentioned polymerizer, it is preferable that a reflux capacitor is attached.
本発明の方法によれば、塩化ビニル単量体又は塩化ビニル単量体及び塩化ビニル単量体と共重合可能な単量体の混合物を水性媒体中で重合し、塩化ビニル系重合体を製造する際に、重合反応液が実質的には発泡することなく、かつ品質の安定した塩化ビニル系重合体を製造することができる。
According to the method of the present invention, a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer is polymerized in an aqueous medium to produce a vinyl chloride polymer. At that time, the polymerization reaction solution does not substantially foam, and a vinyl chloride-based polymer having stable quality can be produced.
以下、本発明について詳述する。
Hereinafter, the present invention will be described in detail.
＜単量体＞
本発明で用いられる単量体原料は、塩化ビニル単量体、又は塩化ビニル単量体を主成分とする単量体混合物である。この塩化ビニル単量体を主成分とする単量体混合物は、少なくとも５０重量％以上、好ましくは８０重量％以上の塩化ビニル単量体と、塩化ビニル単量体と共重合可能な他の単量体とからなる混合物である。ここで用いられる塩化ビニル単量体と共重合可能な他の単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル等のビニルエステル；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等の（メタ）アクリル酸エステル；エチレン、プロピレン等のオレフィン；無水マレイン酸；アクリロニトリル；スチレン；及び塩化ビニリデン等の単量体が挙げられる。これらの単量体は、一種単独で用いても、二種以上を組み合わせて用いてもよい。 <Monomer>
The monomer raw material used in the present invention is a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer as a main component. The monomer mixture containing the vinyl chloride monomer as a main component contains at least 50% by weight or more, preferably 80% by weight or more of the vinyl chloride monomer and another simple copolymerizable with the vinyl chloride monomer. It is a mixture consisting of a monomer. Examples of other monomers copolymerizable with the vinyl chloride monomer used here include vinyl esters such as vinyl acetate and vinyl propionate; methyl (meth) acrylate, ethyl (meth) acrylate and the like. Examples thereof include (meth) acrylic acid esters; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; and monomers such as vinylidene chloride. These monomers may be used alone or in combination of two or more.
本発明で用いられる単量体原料は、塩化ビニル単量体、又は塩化ビニル単量体を主成分とする単量体混合物である。この塩化ビニル単量体を主成分とする単量体混合物は、少なくとも５０重量％以上、好ましくは８０重量％以上の塩化ビニル単量体と、塩化ビニル単量体と共重合可能な他の単量体とからなる混合物である。ここで用いられる塩化ビニル単量体と共重合可能な他の単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル等のビニルエステル；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等の（メタ）アクリル酸エステル；エチレン、プロピレン等のオレフィン；無水マレイン酸；アクリロニトリル；スチレン；及び塩化ビニリデン等の単量体が挙げられる。これらの単量体は、一種単独で用いても、二種以上を組み合わせて用いてもよい。 <Monomer>
The monomer raw material used in the present invention is a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer as a main component. The monomer mixture containing the vinyl chloride monomer as a main component contains at least 50% by weight or more, preferably 80% by weight or more of the vinyl chloride monomer and another simple copolymerizable with the vinyl chloride monomer. It is a mixture consisting of a monomer. Examples of other monomers copolymerizable with the vinyl chloride monomer used here include vinyl esters such as vinyl acetate and vinyl propionate; methyl (meth) acrylate, ethyl (meth) acrylate and the like. Examples thereof include (meth) acrylic acid esters; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; and monomers such as vinylidene chloride. These monomers may be used alone or in combination of two or more.
＜共重合ポリエーテルの水溶液＞
本発明には、共重合ポリエーテルの水溶液を用いる。また、本発明では、重量平均分子量が１０００～３５００、好ましくは１１００を超え３２００以下、及び、エチレンオキシドとプロピレンオキシドのモル比（プロピレンオキシドに対するエチレンオキシドのモル比）が１０／９０～６０／４０、好ましくは２０／８０～６０／４０である共重合ポリエーテルを使用する。また、具体的には、共重合ポリエーテルは、エチレンオキシドとプロピレンオキシドとを上記のモル比で重合した共重合体であり、エチレンオキシド由来の構成単位とプロピレンオキシド由来の構成単位とを有する。なお、重量平均分子量は、スチレン換算によるＧＰＣ測定で行う。 <Aqueous solution of copolymerized polyether>
An aqueous solution of a copolymerized polyether is used in the present invention. Further, in the present invention, the weight average molecular weight is 1000 to 3500, preferably more than 1100 and 3200 or less, and the molar ratio of ethylene oxide to propylene oxide (molar ratio of ethylene oxide to propylene oxide) is 10/90 to 60/40, preferably. Uses a copolymerized polyether that is 20/80 to 60/40. Specifically, the copolymerized polyether is a copolymer obtained by polymerizing ethylene oxide and propylene oxide in the above molar ratio, and has a structural unit derived from ethylene oxide and a structural unit derived from propylene oxide. The weight average molecular weight is measured by GPC in terms of styrene.
本発明には、共重合ポリエーテルの水溶液を用いる。また、本発明では、重量平均分子量が１０００～３５００、好ましくは１１００を超え３２００以下、及び、エチレンオキシドとプロピレンオキシドのモル比（プロピレンオキシドに対するエチレンオキシドのモル比）が１０／９０～６０／４０、好ましくは２０／８０～６０／４０である共重合ポリエーテルを使用する。また、具体的には、共重合ポリエーテルは、エチレンオキシドとプロピレンオキシドとを上記のモル比で重合した共重合体であり、エチレンオキシド由来の構成単位とプロピレンオキシド由来の構成単位とを有する。なお、重量平均分子量は、スチレン換算によるＧＰＣ測定で行う。 <Aqueous solution of copolymerized polyether>
An aqueous solution of a copolymerized polyether is used in the present invention. Further, in the present invention, the weight average molecular weight is 1000 to 3500, preferably more than 1100 and 3200 or less, and the molar ratio of ethylene oxide to propylene oxide (molar ratio of ethylene oxide to propylene oxide) is 10/90 to 60/40, preferably. Uses a copolymerized polyether that is 20/80 to 60/40. Specifically, the copolymerized polyether is a copolymer obtained by polymerizing ethylene oxide and propylene oxide in the above molar ratio, and has a structural unit derived from ethylene oxide and a structural unit derived from propylene oxide. The weight average molecular weight is measured by GPC in terms of styrene.
前記分子量が１０００未満であると、重合系に生じた泡の界面張力を低下させて破泡する作用が小さくなるので、重合中の消泡効果が十分でなく、使用量を増大させる必要が生じ、得られる重合体の品質に影響を及ぼすという問題がある。また、３５００を超えると、特に大型重合器において、上記共重合ポリエーテルが拡散しにくく消泡効果が低下して、品質劣化した塩化ビニル重合体が得られてしまう。
When the molecular weight is less than 1000, the action of lowering the interfacial tension of bubbles generated in the polymerization system and breaking the bubbles is reduced, so that the defoaming effect during polymerization is not sufficient and it is necessary to increase the amount used. There is a problem that it affects the quality of the obtained polymer. On the other hand, if it exceeds 3500, the copolymerized polyether is difficult to diffuse and the defoaming effect is lowered, particularly in a large polymer, and a vinyl chloride polymer having deteriorated quality is obtained.
エチレンオキシドとプロピレンオキシドのモル比が上記範囲以外の場合、消泡効果が低下する或いは反対に泡立ってしまうという問題が生じる。
If the molar ratio of ethylene oxide to propylene oxide is out of the above range, there is a problem that the defoaming effect is reduced or conversely foaming occurs.
また、エチレンオキシドとプロピレンオキシドの共重合ポリエーテルは、ブロック共重合体でもランダム共重合体でもよい。
Further, the copolymerized polyether of ethylene oxide and propylene oxide may be a block copolymer or a random copolymer.
なお、エチレンオキシドとプロピレンオキシドの共重合ポリエーテルは、水溶液の状態で使用することが好ましく、固形分０．１ｗｔ％～５０ｗｔ％になるように調整する。また、この際、必要により有機溶媒としてエタノール等を配合しても構わない。言い換えると、本発明においては、有機溶媒を含む共重合ポリエーテルの溶液を用いてもよい。
The copolymerized polyether of ethylene oxide and propylene oxide is preferably used in an aqueous solution state, and is adjusted so that the solid content is 0.1 wt% to 50 wt%. At this time, ethanol or the like may be blended as an organic solvent if necessary. In other words, in the present invention, a solution of a copolymerized polyether containing an organic solvent may be used.
前記共重合ポリエーテルは、仕込み塩化ビニル単量体に対して、０.００５～０.０５０重量部、好ましくは０.０１０～０.０３０重量部を使用し、重合反応系に水溶液として添加される。仕込み塩化ビニル単量体に対する共重合ポリエーテルの使用量が、０.００５重量部未満であると、消泡効果を十分に生じさせることができない。また、０.０５０重量部を超えると、使用量が増大して経済的に不利になるだけでなく、重合器壁面にスケールが付着しやすくなり、フィッシュアイが増加する恐れがある。該共重合ポリエーテルは、上述のように、濃度が、通常、０.１～５０重量％、好ましくは０.５～２０重量％の水溶液として、重合反応系に添加する。
The copolymerized polyether is added as an aqueous solution to the polymerization reaction system using 0.005 to 0.050 parts by weight, preferably 0.010 to 0.030 parts by weight, based on the charged vinyl chloride monomer. To. If the amount of the copolymerized polyether used with respect to the charged vinyl chloride monomer is less than 0.005 parts by weight, the defoaming effect cannot be sufficiently produced. On the other hand, if it exceeds 0.050 parts by weight, not only the amount used increases, which is economically disadvantageous, but also scale tends to adhere to the wall surface of the polymer, which may increase fish eyes. As described above, the copolymerized polyether is added to the polymerization reaction system as an aqueous solution having a concentration of usually 0.1 to 50% by weight, preferably 0.5 to 20% by weight.
共重合ポリエーテル水溶液は、重合率が３０～８０％、好ましくは６０～８０％の範囲内であるときに添加されることがよい。前記添加時期が、重合率３０％になる前の時点である場合は、重合体の粒子形成が不十分な時期であるため、添加により粒度分布に悪影響を与える場合がある。また、重合率が８０％を超えている時点では、すでに、発泡のピークを過ぎているため、重合反応液がコンデンサー内まで吹き上げて重合体粒子がコンデンサー内に堆積してしまっている恐れがあり、消泡剤添加の効果が小さくなる。
The copolymerized polyether aqueous solution may be added when the polymerization rate is in the range of 30 to 80%, preferably 60 to 80%. When the addition time is before the polymerization rate reaches 30%, the particle formation of the polymer is insufficient, and the addition may adversely affect the particle size distribution. Further, when the polymerization rate exceeds 80%, the foaming peak has already passed, so that the polymerization reaction solution may be blown up into the capacitor and the polymer particles may be deposited in the capacitor. , The effect of adding antifoaming agent becomes small.
＜水性媒体＞
水性媒体としては、上水、脱イオン水、蒸留水、超純水等の水、水と水溶性有機溶媒との混合媒体などが挙げられる。上記水溶性有機溶媒としては、たとえばメタノール、エタノール、ｎ－プロパノール、イソプロパノール、エチレングリコール、ジエチレングリコールなどのアルコールが挙げられる。水性媒体が混合媒体である場合、水系媒体中の水溶性有機溶媒の含有量は、好ましくは０質量％を超え５０質量％以下である。 <Aqueous medium>
Examples of the aqueous medium include clean water, deionized water, distilled water, water such as ultrapure water, and a mixed medium of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and diethylene glycol. When the aqueous medium is a mixed medium, the content of the water-soluble organic solvent in the aqueous medium is preferably more than 0% by mass and 50% by mass or less.
水性媒体としては、上水、脱イオン水、蒸留水、超純水等の水、水と水溶性有機溶媒との混合媒体などが挙げられる。上記水溶性有機溶媒としては、たとえばメタノール、エタノール、ｎ－プロパノール、イソプロパノール、エチレングリコール、ジエチレングリコールなどのアルコールが挙げられる。水性媒体が混合媒体である場合、水系媒体中の水溶性有機溶媒の含有量は、好ましくは０質量％を超え５０質量％以下である。 <Aqueous medium>
Examples of the aqueous medium include clean water, deionized water, distilled water, water such as ultrapure water, and a mixed medium of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and diethylene glycol. When the aqueous medium is a mixed medium, the content of the water-soluble organic solvent in the aqueous medium is preferably more than 0% by mass and 50% by mass or less.
＜分散剤＞
前述の塩化ビニル、又は塩化ビニルを含む単量体混合物を水性媒体中で重合する場合に通常使用される分散剤は、特に限定されず、従来の塩化ビニル系重合体の製造に使用されるもので差し支えない。この分散剤としては、例えば、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース等の水溶性セルロースエーテル；水溶性部分鹸化ポリビニルアルコール；アクリル酸重合体；ゼラチン等の水溶性ポリマー；ソルビタンモノラウレート、ソルビタントリオレート、グリセリントリステアレート、エチレンオキシド－プロピレンオキシドブロック共重合体等の油溶性乳化剤；及びポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレングリセリンオレート、ラウリン酸ナトリウム等の水溶性乳化剤等が挙げられる。これらは、一種単独で用いても、二種以上を組み合わせて用いてもよく、使用量は仕込み塩化ビニル単量体１００質量部に対して、好ましくは０.０１０～０.２００重量部、さらに好ましくは０．０３０～０．１５質量部である。 <Dispersant>
The dispersant usually used when polymerizing the above-mentioned vinyl chloride or a monomer mixture containing vinyl chloride in an aqueous medium is not particularly limited, and is used for producing a conventional vinyl chloride-based polymer. It doesn't matter. Examples of the dispersant include water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose; water-soluble partially saponified polyvinyl alcohols; acrylic acid polymers; water-soluble polymers such as gelatin; sorbitan monolaurate. , Oil-soluble emulsifiers such as sorbitan triolate, glycerin tristearate, ethylene oxide-propylene oxide block copolymer; and water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, sodium laurate, etc. Be done. These may be used alone or in combination of two or more, and the amount used is preferably 0.010 to 0.200 parts by weight, more preferably 0.010 to 0.200 parts by mass, based on 100 parts by mass of the charged vinyl chloride monomer. It is preferably 0.030 to 0.15 parts by mass.
前述の塩化ビニル、又は塩化ビニルを含む単量体混合物を水性媒体中で重合する場合に通常使用される分散剤は、特に限定されず、従来の塩化ビニル系重合体の製造に使用されるもので差し支えない。この分散剤としては、例えば、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース等の水溶性セルロースエーテル；水溶性部分鹸化ポリビニルアルコール；アクリル酸重合体；ゼラチン等の水溶性ポリマー；ソルビタンモノラウレート、ソルビタントリオレート、グリセリントリステアレート、エチレンオキシド－プロピレンオキシドブロック共重合体等の油溶性乳化剤；及びポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレングリセリンオレート、ラウリン酸ナトリウム等の水溶性乳化剤等が挙げられる。これらは、一種単独で用いても、二種以上を組み合わせて用いてもよく、使用量は仕込み塩化ビニル単量体１００質量部に対して、好ましくは０.０１０～０.２００重量部、さらに好ましくは０．０３０～０．１５質量部である。 <Dispersant>
The dispersant usually used when polymerizing the above-mentioned vinyl chloride or a monomer mixture containing vinyl chloride in an aqueous medium is not particularly limited, and is used for producing a conventional vinyl chloride-based polymer. It doesn't matter. Examples of the dispersant include water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose; water-soluble partially saponified polyvinyl alcohols; acrylic acid polymers; water-soluble polymers such as gelatin; sorbitan monolaurate. , Oil-soluble emulsifiers such as sorbitan triolate, glycerin tristearate, ethylene oxide-propylene oxide block copolymer; and water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, sodium laurate, etc. Be done. These may be used alone or in combination of two or more, and the amount used is preferably 0.010 to 0.200 parts by weight, more preferably 0.010 to 0.200 parts by mass, based on 100 parts by mass of the charged vinyl chloride monomer. It is preferably 0.030 to 0.15 parts by mass.
＜重合開始剤＞
さらに、通常使用される重合開始剤は、特に限定されず、従来の塩化ビニル系重合体の製造に使用されるもので差し支えない。この重合開始剤としては、例えば、ジイソプロピルパーオキシジカーボネート、ビス（２－エチルヘキシル）パーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネート等のパーオキシカーボネート化合物；ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ヘキシルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシネオデカネート、α－クミルパーオキシネオデカネート等のパーオキシエステル化合物；アセチルシクロヘキシルスルホニルパーオキシド、２，４，４－トリメチルペンチル－２－パーオキシフェノキシアセテート、３，５，５－トリメチルヘキサノイルパーオキシド等の過酸化物；アゾビス（２，４－ジメチルバレロニトリル）、アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）等のアゾ化合物；過硫酸カリウム；過硫酸アンモニウム；及び過酸化水素等が挙げられる。これらは、一種単独で用いても、二種以上を組み合わせて用いてもよく、使用量は仕込み塩化ビニル単量体１００質量部に対して、好ましくは０.０１０～０.２００重量部、さらに好ましくは０．０３～０．１５質量部である。 <Polymer initiator>
Further, the polymerization initiator which is usually used is not particularly limited, and may be one used in the production of a conventional vinyl chloride polymer. Examples of the polymerization initiator include peroxycarbonate compounds such as diisopropylperoxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, and diethoxyethylperoxydicarbonate; tert-butylperoxypivalate, tert-. Peroxy ester compounds such as hexyl peroxypivalate, tert-butyl peroxyneodecanate, α-cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxy Peroxides such as acetate, 3,5,5-trimethylhexanoyl peroxide; azo compounds such as azobis (2,4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile); Examples thereof include potassium sulfate; ammonium persulfate; and hydrogen peroxide. These may be used alone or in combination of two or more, and the amount used is preferably 0.010 to 0.200 parts by weight, more preferably 0.010 to 0.200 parts by mass, based on 100 parts by mass of the charged vinyl chloride monomer. It is preferably 0.03 to 0.15 parts by mass.
さらに、通常使用される重合開始剤は、特に限定されず、従来の塩化ビニル系重合体の製造に使用されるもので差し支えない。この重合開始剤としては、例えば、ジイソプロピルパーオキシジカーボネート、ビス（２－エチルヘキシル）パーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネート等のパーオキシカーボネート化合物；ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ヘキシルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシネオデカネート、α－クミルパーオキシネオデカネート等のパーオキシエステル化合物；アセチルシクロヘキシルスルホニルパーオキシド、２，４，４－トリメチルペンチル－２－パーオキシフェノキシアセテート、３，５，５－トリメチルヘキサノイルパーオキシド等の過酸化物；アゾビス（２，４－ジメチルバレロニトリル）、アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）等のアゾ化合物；過硫酸カリウム；過硫酸アンモニウム；及び過酸化水素等が挙げられる。これらは、一種単独で用いても、二種以上を組み合わせて用いてもよく、使用量は仕込み塩化ビニル単量体１００質量部に対して、好ましくは０.０１０～０.２００重量部、さらに好ましくは０．０３～０．１５質量部である。 <Polymer initiator>
Further, the polymerization initiator which is usually used is not particularly limited, and may be one used in the production of a conventional vinyl chloride polymer. Examples of the polymerization initiator include peroxycarbonate compounds such as diisopropylperoxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, and diethoxyethylperoxydicarbonate; tert-butylperoxypivalate, tert-. Peroxy ester compounds such as hexyl peroxypivalate, tert-butyl peroxyneodecanate, α-cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxy Peroxides such as acetate, 3,5,5-trimethylhexanoyl peroxide; azo compounds such as azobis (2,4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile); Examples thereof include potassium sulfate; ammonium persulfate; and hydrogen peroxide. These may be used alone or in combination of two or more, and the amount used is preferably 0.010 to 0.200 parts by weight, more preferably 0.010 to 0.200 parts by mass, based on 100 parts by mass of the charged vinyl chloride monomer. It is preferably 0.03 to 0.15 parts by mass.
＜酸化防止剤＞
また、通常使用される酸化防止剤は特に限定されず、塩化ビニル系重合体の製造に一般に使用されるもので差し支えない。この酸化防止剤としては、例えば、２，２－ビス（４－ヒドロキシフェニル）プロパン、ヒドロキノン、ｐ－メトキシフェノール、ｔｅｒｔ－ブチル－ヒドロキシアニソール、ｎ－オクタデシル－３－（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェニル）プロピオネート、ｔｅｒｔ－ブチルヒドロキノン、２，５－ジ－ｔｅｒｔ－ブチルヒドロキノン、４，４’－ブチリデン－ビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン、２，２’－メチレン－ビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、トリエチレングリコール－ビス［３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，６－ジ－ｔｅｒｔ－ブチル－４－ｓｅｃ－ブチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、４－ｔｅｒｔ－ブチルカテコール、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、トコフェロール、ノルジヒドログアイアレチン酸等のフェノール化合物；セミカルバジド、１－アセチルセミカルバジド、１－クロロアセチルセミカルバジド、１－ジクロロアセチルセミカルバジド、１－ベンゾイルセミカルバジド、セミカルバゾン等のセミカルバジド誘導体；カルボヒドラジド、チオセミカルバジド、チオセミカルバゾン等のチオカルバジドの誘導体；Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、４，４’－ビス（２，４－ジメチルベンジル）ジフェニルアミン等のアミン化合物；４－ニトロアニソール、Ｎ－ニトロソジフェニルアミン、４－ニトロアニリン、Ｎ－ニトロソフェニルヒドロキシリルアミンアルミニウム塩等のニトロ化合物又はニトロソ化合物；トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、４，４’－ブチリデン－ビス（３－メチル－６－ｔｅｒｔ－ブチルフェニル－ジ－トリデシルホスファイト）、サイクリックネオペンタンテトライルビス（オクタデシルホスファイト）、トリス（ノニルフェニル）ホスファイト、トリス（ジノニルフェニル）ホスファイト等のリン化合物；スチレン、１，３－ヘキサジエン、α－メチルスチレン等の不飽和炭化水素化合物；及びジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオジプロピオネート、ドデシルメルカプタン、１，３－ジフェニル－２－チオ尿素等の硫黄化合物等が挙げられる。 <Antioxidant>
Further, the antioxidant which is usually used is not particularly limited, and may be one which is generally used for producing a vinyl chloride polymer. Examples of this antioxidant include 2,2-bis (4-hydroxyphenyl) propane, hydroquinone, p-methoxyphenol, tert-butyl-hydroxyanisole, and n-octadecyl-3- (4-hydroxy-3,5). -Di-tert-butylphenyl) propionate, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 3,5- Di-tert-butyl-4-hydroxytoluene, 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-) 4-Hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-sec-butylphenol , 2,6-di-tert-butyl-4-methylphenol, 4-tert-butylcatechol, 4,4'-thiobis (6-tert-butyl-m-cresol), tocopherol, nordihydroguairetic acid, etc. Phenol compounds; semicarbazide derivatives such as semicarbazide, 1-acetylsemicarbazide, 1-chloroacetylsemicarbazide, 1-dichloroacetylsemicarbazide, 1-benzoylsemicarbazide, semicarbazone; derivatives of thiocarbazide such as carbohydrazide, thiosemicarbazide, thiosemicarbazide; Amin compounds such as N, N'-diphenyl-p-phenylenediamine, 4,4'-bis (2,4-dimethylbenzyl) diphenylamine; 4-nitroanisole, N-nitrosodiphenylamine, 4-nitroaniline, N-nitroso Nitro compounds or nitroso compounds such as phenylhydroxylylamine aluminum salts; triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl- Di-tridecylphosphite), cyclic neopentantetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite and other phosphorus compounds; styrene, 1,3-hexadiene, Unsaturated hydrocarbon compounds such as α-methylstyrene; Examples thereof include sulfur compounds such as dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, dodecyl mercaptan, and 1,3-diphenyl-2-thiourea.
また、通常使用される酸化防止剤は特に限定されず、塩化ビニル系重合体の製造に一般に使用されるもので差し支えない。この酸化防止剤としては、例えば、２，２－ビス（４－ヒドロキシフェニル）プロパン、ヒドロキノン、ｐ－メトキシフェノール、ｔｅｒｔ－ブチル－ヒドロキシアニソール、ｎ－オクタデシル－３－（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェニル）プロピオネート、ｔｅｒｔ－ブチルヒドロキノン、２，５－ジ－ｔｅｒｔ－ブチルヒドロキノン、４，４’－ブチリデン－ビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン、２，２’－メチレン－ビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、トリエチレングリコール－ビス［３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，６－ジ－ｔｅｒｔ－ブチル－４－ｓｅｃ－ブチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、４－ｔｅｒｔ－ブチルカテコール、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、トコフェロール、ノルジヒドログアイアレチン酸等のフェノール化合物；セミカルバジド、１－アセチルセミカルバジド、１－クロロアセチルセミカルバジド、１－ジクロロアセチルセミカルバジド、１－ベンゾイルセミカルバジド、セミカルバゾン等のセミカルバジド誘導体；カルボヒドラジド、チオセミカルバジド、チオセミカルバゾン等のチオカルバジドの誘導体；Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、４，４’－ビス（２，４－ジメチルベンジル）ジフェニルアミン等のアミン化合物；４－ニトロアニソール、Ｎ－ニトロソジフェニルアミン、４－ニトロアニリン、Ｎ－ニトロソフェニルヒドロキシリルアミンアルミニウム塩等のニトロ化合物又はニトロソ化合物；トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、４，４’－ブチリデン－ビス（３－メチル－６－ｔｅｒｔ－ブチルフェニル－ジ－トリデシルホスファイト）、サイクリックネオペンタンテトライルビス（オクタデシルホスファイト）、トリス（ノニルフェニル）ホスファイト、トリス（ジノニルフェニル）ホスファイト等のリン化合物；スチレン、１，３－ヘキサジエン、α－メチルスチレン等の不飽和炭化水素化合物；及びジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオジプロピオネート、ドデシルメルカプタン、１，３－ジフェニル－２－チオ尿素等の硫黄化合物等が挙げられる。 <Antioxidant>
Further, the antioxidant which is usually used is not particularly limited, and may be one which is generally used for producing a vinyl chloride polymer. Examples of this antioxidant include 2,2-bis (4-hydroxyphenyl) propane, hydroquinone, p-methoxyphenol, tert-butyl-hydroxyanisole, and n-octadecyl-3- (4-hydroxy-3,5). -Di-tert-butylphenyl) propionate, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 3,5- Di-tert-butyl-4-hydroxytoluene, 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-) 4-Hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-sec-butylphenol , 2,6-di-tert-butyl-4-methylphenol, 4-tert-butylcatechol, 4,4'-thiobis (6-tert-butyl-m-cresol), tocopherol, nordihydroguairetic acid, etc. Phenol compounds; semicarbazide derivatives such as semicarbazide, 1-acetylsemicarbazide, 1-chloroacetylsemicarbazide, 1-dichloroacetylsemicarbazide, 1-benzoylsemicarbazide, semicarbazone; derivatives of thiocarbazide such as carbohydrazide, thiosemicarbazide, thiosemicarbazide; Amin compounds such as N, N'-diphenyl-p-phenylenediamine, 4,4'-bis (2,4-dimethylbenzyl) diphenylamine; 4-nitroanisole, N-nitrosodiphenylamine, 4-nitroaniline, N-nitroso Nitro compounds or nitroso compounds such as phenylhydroxylylamine aluminum salts; triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl- Di-tridecylphosphite), cyclic neopentantetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite and other phosphorus compounds; styrene, 1,3-hexadiene, Unsaturated hydrocarbon compounds such as α-methylstyrene; Examples thereof include sulfur compounds such as dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, dodecyl mercaptan, and 1,3-diphenyl-2-thiourea.
中でも、得られる重合体の抗初期着色性（重合体を成形加工した際に着色が生じにくい性質）が良好で、重合器へのスケール付着が少ない点で、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシトルエン、トリエチレングリコール－ビス［３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、ｔｅｒｔ－ブチルヒドロキシアニソール、ｔｅｒｔ－ブチルヒドロキノン、２，６－ジ－ｔｅｒｔ－ブチル－４－ｓｅｃ－ブチルフェノール及びオクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネートが好ましい。これらは、一種単独で用いても、二種以上を組み合わせて用いてもよい。また、これら酸化防止剤の使用量は仕込み塩化ビニル単量体１００質量部に対して、好ましくは０.０５０重量部以下、０質量部以上である。
Among them, 3,5-di-tert-butyl has good anti-initial colorability (property that coloring does not easily occur when the polymer is molded) and little scale adhesion to the polymer. -4-Hydroxytoluene, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], tert-butylhydroxyanisole, tert-butylhydroquinone, 2,6-di- Preferably, tert-butyl-4-sec-butylphenol and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. These may be used alone or in combination of two or more. The amount of these antioxidants used is preferably 0.050 parts by weight or less and 0 parts by mass or more with respect to 100 parts by mass of the charged vinyl chloride monomer.
＜その他の任意成分＞
本発明の方法において、必要に応じて、塩化ビニル系重合体の製造に一般的に使用されている重合度調整剤、連鎖移動剤、ゲル化改良剤、帯電防止剤等を適宜使用してもよい。また、酸化防止剤を重合反応の制御、生成した重合体の劣化防止等の目的で、重合開始前、重合中あるいは重合終了に重合系に添加してもよい。 <Other optional ingredients>
In the method of the present invention, if necessary, a degree of polymerization adjusting agent, a chain transfer agent, a gelation improving agent, an antistatic agent, etc., which are generally used for producing a vinyl chloride polymer, may be appropriately used. Good. Further, an antioxidant may be added to the polymerization system before the start of the polymerization, during the polymerization or at the end of the polymerization for the purpose of controlling the polymerization reaction and preventing the deterioration of the produced polymer.
本発明の方法において、必要に応じて、塩化ビニル系重合体の製造に一般的に使用されている重合度調整剤、連鎖移動剤、ゲル化改良剤、帯電防止剤等を適宜使用してもよい。また、酸化防止剤を重合反応の制御、生成した重合体の劣化防止等の目的で、重合開始前、重合中あるいは重合終了に重合系に添加してもよい。 <Other optional ingredients>
In the method of the present invention, if necessary, a degree of polymerization adjusting agent, a chain transfer agent, a gelation improving agent, an antistatic agent, etc., which are generally used for producing a vinyl chloride polymer, may be appropriately used. Good. Further, an antioxidant may be added to the polymerization system before the start of the polymerization, during the polymerization or at the end of the polymerization for the purpose of controlling the polymerization reaction and preventing the deterioration of the produced polymer.
＜その他の条件＞
また、重合における他の条件、例えば、重合器への水性媒体、塩化ビニル単量体又は塩化ビニル単量体を含む単量体混合物、分散助剤、重合開始剤等の仕込み方法、仕込み割合、並びに重合温度等は従来の条件と同様で差し支えない。 <Other conditions>
In addition, other conditions in the polymerization, for example, an aqueous medium in the polymerizer, a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer, a dispersion aid, a method of charging a polymerization initiator and the like, a charging ratio, and the like. In addition, the polymerization temperature and the like may be the same as the conventional conditions.
また、重合における他の条件、例えば、重合器への水性媒体、塩化ビニル単量体又は塩化ビニル単量体を含む単量体混合物、分散助剤、重合開始剤等の仕込み方法、仕込み割合、並びに重合温度等は従来の条件と同様で差し支えない。 <Other conditions>
In addition, other conditions in the polymerization, for example, an aqueous medium in the polymerizer, a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer, a dispersion aid, a method of charging a polymerization initiator and the like, a charging ratio, and the like. In addition, the polymerization temperature and the like may be the same as the conventional conditions.
重合器は、特に形状、大きさ等の制限はなく、一般的にＳＵＳ等の耐久性のある重合器を用いればよく、生産性の観点から、容量が好ましくは５０ｍ3以上、更に好ましくは８０ｍ3以上の重合器を用いて重合すればよく、該大型重合器の場合には、特に重合器に還流コンデンサーを併設させることが好ましい。
The polymerizer is not particularly limited in shape, size, etc., and a durable polymerizer such as SUS may be generally used. From the viewpoint of productivity, the capacity is preferably 50 m 3 or more, more preferably 80 m. Polymerization may be carried out using three or more polymerizers, and in the case of the large-scale polymerizer, it is particularly preferable to provide a reflux capacitor in the polymerizer.
上記重合工程としては、たとえば懸濁重合により行われる。この際、塩化ビニル単量体（又は、塩化ビニル単量体混合物）は、ジャケット付重合反応器（重合器）に仕込んだ後、ジャケットに温水を供給することにより重合反応が開始される。重合反応開始後は、ジャケットに冷水を供給して、重合反応温度を一定に維持する。ジャケットによる除熱に加えて、還流コンデンサーへの冷水の供給を開始して、重合を行う。
The polymerization step is, for example, suspension polymerization. At this time, the vinyl chloride monomer (or the vinyl chloride monomer mixture) is charged into a polymerization reactor with a jacket (polymerizer), and then the polymerization reaction is started by supplying warm water to the jacket. After the start of the polymerization reaction, cold water is supplied to the jacket to keep the polymerization reaction temperature constant. In addition to heat removal by the jacket, the supply of cold water to the reflux condenser is started to carry out the polymerization.
より具体的には、重合条件は、特に限定されないが、たとえば、重合器内に、上記ビニル系単量体、その他上記添加剤、懸濁剤（セルロース、ＰＶＡ等の水溶性高分子）および水性媒体を仕込んだ後、重合器の内容物を攪拌しながら昇温して重合反応を行う。具体的には、２０～８０℃で１～２０時間、重合反応を行う。なお、攪拌条件は適宜調整すればよいが、回転数１０ｒｐｍ～３００ｒｐｍ、好ましくは５０～２００ｒｐｍの間で調整しながら重合を行う。
More specifically, the polymerization conditions are not particularly limited, but for example, the vinyl-based monomer, other additives, suspending agents (water-soluble polymers such as cellulose and PVA) and aqueous components are placed in the polymerizer. After charging the medium, the contents of the polymerizer are heated while stirring to carry out the polymerization reaction. Specifically, the polymerization reaction is carried out at 20 to 80 ° C. for 1 to 20 hours. The stirring conditions may be adjusted as appropriate, but the polymerization is carried out while adjusting the rotation speed between 10 rpm and 300 rpm, preferably 50 and 200 rpm.
なお、上記共重合ポリエーテルの水溶液の添加は、上述のように、塩化ビニル（又は塩化ビニル単量体混合物）の重合率が３０％～８０％、好ましくは６０％～８０％において行うことがよい。なお、重合率とは、得られた塩化ビニル樹脂（塩化ビニル系重合体）と仕込んだ塩化ビニル単量体（又は塩化ビニル単量体混合物）の総量との比である。
The addition of the aqueous solution of the copolymerized polyether is carried out when the polymerization rate of vinyl chloride (or vinyl chloride monomer mixture) is 30% to 80%, preferably 60% to 80%, as described above. Good. The polymerization rate is the ratio of the obtained vinyl chloride resin (vinyl chloride-based polymer) to the total amount of the charged vinyl chloride monomer (or vinyl chloride monomer mixture).
なお、重合率が３０％未満で添加した場合、重合が不安定になる恐れがある。一方、重合率が８０％以上で添加した場合、既に泡レベルがピークを過ぎてしまっている或いはピークに近いレベルまで到達してしまっている為、効果が小さくなる場合がある。
If the polymerization rate is less than 30%, the polymerization may become unstable. On the other hand, when the polymerization rate is 80% or more, the foam level has already passed the peak or has reached a level close to the peak, so that the effect may be reduced.
また、添加方法としては任意であり、一度に添加しても徐々に添加しても構わない。
The addition method is arbitrary, and it may be added all at once or gradually.
ところで、近年進められてきている大型化された重合器においては、特許文献１の方法では消泡剤の重量平均分子量が大き過ぎるため、重合器中での拡散がしにくく十分な消泡効果が得られていない。一方、本発明においては、特定の重合段階で、特定の重量平均分子量を有する共重合ポリエーテルを特定の量で添加する。このため、大型重合器の場合であっても、更に、還流コンデンサーを付設した場合であっても、共重合ポリエーテルが重合器中で十分に拡散でき、消泡効果が得られる。また、得られた塩化ビニル系重合体の品質にも悪影響を与えることはない。
By the way, in the large-sized polymerizer that has been promoted in recent years, the method of Patent Document 1 has an excessively large weight average molecular weight of the defoaming agent, so that it is difficult to diffuse in the polymerizer and a sufficient defoaming effect is obtained. Not obtained. On the other hand, in the present invention, a copolymerized polyether having a specific weight average molecular weight is added in a specific amount at a specific polymerization step. Therefore, even in the case of a large-scale polymerizer or when a reflux capacitor is attached, the copolymerized polyether can be sufficiently diffused in the polymerizer, and a defoaming effect can be obtained. In addition, the quality of the obtained vinyl chloride polymer is not adversely affected.
以下、実施例等を挙げて本発明を更に詳細に説明するが、本発明はこれらのものに限定されない。なお、以下に述べる「％」は、特に断らない限り、「重量％」を意味とし、重合率は予め重合を行い重合時間と重合率との関係を求めた結果を基準とする。本発明は、分散性、消泡性、及び壁面へのＰＶＣ付着量によって評価した。
Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these. Unless otherwise specified, "%" described below means "% by weight", and the polymerization rate is based on the result of performing polymerization in advance and determining the relationship between the polymerization time and the polymerization rate. The present invention was evaluated by dispersibility, defoaming property, and amount of PVC adhered to the wall surface.
（実施例１）
還流コンデンサー及び泡センサーを付した内容積１００ｍ3のステンレス製重合器内に、脱イオン水４９．０ｔ、鹸化度８０モル％の部分鹸化ポリビニルアルコール１９．１ｋｇ、並びにメトキシ置換度が２８．５重量％及びヒドロキシルプロピル置換基が８．９重量％のヒドロキシメチルセルロース７．１５ｋｇを仕込んだ後、所定量の塩化ビニル単量体３５．０ｔを仕込んだ。重合開始剤としてビス（２－エチルヘキシル）パーオキシジカーボネート１７．５ｋｇを仕込み、同時にジャケットに温水を通して昇温を開始し、重合器内が５７．０℃まで昇温したところで、その温度を保ち２５０ｒｐｍの回転数で重合を続けた。
重合率が７０％に到達した時点で、重量平均分子量が３２００、及び、エチレンオキシドとプロピレンオキシドのモル比が６０／４０である共重合ポリエーテルの１％水溶液を、３５０ｋｇ添加した。その後、重合反応器内の圧力が０．５８８ＭＰａ・Ｇ（４，４１０ｍｍＨｇ）に降圧した時点（重合率８６％）まで反応を行い、その後、重合器内にトリエチレングリコール－ビス［３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］の３０％水性分散液を３５ｋｇ添加し、未反応の単量体を回収した。得られた重合体スラリー中に２５％アンモニア水１０ｋｇを添加してｐＨを調整後、重合体スラリーを脱水及び乾燥することにより、塩化ビニル重合体を得た。特に粒度分布、嵩比重、ポロシティにおいて問題はなかった。 (Example 1)
In a stainless steel polymerizer with an internal volume of 100 m 3 equipped with a reflux condenser and a foam sensor, 49.0 tons of deionized water, 19.1 kg of partially saponified polyvinyl alcohol having a saponification degree of 80 mol%, and a methoxy substitution degree of 28.5 weight. % And 7.15 kg of hydroxymethyl cellulose having a hydroxylpropyl substituent of 8.9% by weight were charged, and then a predetermined amount of vinyl chloride monomer (35.0 tons) was charged. 17.5 kg of bis (2-ethylhexyl) peroxydicarbonate was charged as a polymerization initiator, and at the same time, warm water was passed through the jacket to start raising the temperature. When the temperature inside the polymer was raised to 57.0 ° C, the temperature was maintained at 250 rpm. The polymerization was continued at the rotation speed of.
When the polymerization rate reached 70%, 350 kg of a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 3200 and a molar ratio of ethylene oxide to propylene oxide of 60/40 was added. After that, the reaction was carried out until the pressure in the polymerization reactor was lowered to 0.588 MPa · G (4,410 mmHg) (polymerization rate 86%), and then triethylene glycol-bis [3- (3) was placed in the polymerizer. -Tert-Butyl-5-methyl-4-hydroxyphenyl) propionate] 30% aqueous dispersion was added, and the unreacted monomer was recovered. A vinyl chloride polymer was obtained by adding 10 kg of 25% aqueous ammonia to the obtained polymer slurry to adjust the pH, and then dehydrating and drying the polymer slurry. In particular, there were no problems with particle size distribution, bulk specific gravity, and porosity.
還流コンデンサー及び泡センサーを付した内容積１００ｍ3のステンレス製重合器内に、脱イオン水４９．０ｔ、鹸化度８０モル％の部分鹸化ポリビニルアルコール１９．１ｋｇ、並びにメトキシ置換度が２８．５重量％及びヒドロキシルプロピル置換基が８．９重量％のヒドロキシメチルセルロース７．１５ｋｇを仕込んだ後、所定量の塩化ビニル単量体３５．０ｔを仕込んだ。重合開始剤としてビス（２－エチルヘキシル）パーオキシジカーボネート１７．５ｋｇを仕込み、同時にジャケットに温水を通して昇温を開始し、重合器内が５７．０℃まで昇温したところで、その温度を保ち２５０ｒｐｍの回転数で重合を続けた。
重合率が７０％に到達した時点で、重量平均分子量が３２００、及び、エチレンオキシドとプロピレンオキシドのモル比が６０／４０である共重合ポリエーテルの１％水溶液を、３５０ｋｇ添加した。その後、重合反応器内の圧力が０．５８８ＭＰａ・Ｇ（４，４１０ｍｍＨｇ）に降圧した時点（重合率８６％）まで反応を行い、その後、重合器内にトリエチレングリコール－ビス［３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］の３０％水性分散液を３５ｋｇ添加し、未反応の単量体を回収した。得られた重合体スラリー中に２５％アンモニア水１０ｋｇを添加してｐＨを調整後、重合体スラリーを脱水及び乾燥することにより、塩化ビニル重合体を得た。特に粒度分布、嵩比重、ポロシティにおいて問題はなかった。 (Example 1)
In a stainless steel polymerizer with an internal volume of 100 m 3 equipped with a reflux condenser and a foam sensor, 49.0 tons of deionized water, 19.1 kg of partially saponified polyvinyl alcohol having a saponification degree of 80 mol%, and a methoxy substitution degree of 28.5 weight. % And 7.15 kg of hydroxymethyl cellulose having a hydroxylpropyl substituent of 8.9% by weight were charged, and then a predetermined amount of vinyl chloride monomer (35.0 tons) was charged. 17.5 kg of bis (2-ethylhexyl) peroxydicarbonate was charged as a polymerization initiator, and at the same time, warm water was passed through the jacket to start raising the temperature. When the temperature inside the polymer was raised to 57.0 ° C, the temperature was maintained at 250 rpm. The polymerization was continued at the rotation speed of.
When the polymerization rate reached 70%, 350 kg of a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 3200 and a molar ratio of ethylene oxide to propylene oxide of 60/40 was added. After that, the reaction was carried out until the pressure in the polymerization reactor was lowered to 0.588 MPa · G (4,410 mmHg) (polymerization rate 86%), and then triethylene glycol-bis [3- (3) was placed in the polymerizer. -Tert-Butyl-5-methyl-4-hydroxyphenyl) propionate] 30% aqueous dispersion was added, and the unreacted monomer was recovered. A vinyl chloride polymer was obtained by adding 10 kg of 25% aqueous ammonia to the obtained polymer slurry to adjust the pH, and then dehydrating and drying the polymer slurry. In particular, there were no problems with particle size distribution, bulk specific gravity, and porosity.
（実施例２）
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が１,８００、及び、エチレンオキシドとプロピレンオキシドのモル比が４０／６０である共重合ポリエーテルの１％水溶液を用いた。 (Example 2)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 1,800 and a molar ratio of ethylene oxide to propylene oxide of 40/60 was used. There was.
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が１,８００、及び、エチレンオキシドとプロピレンオキシドのモル比が４０／６０である共重合ポリエーテルの１％水溶液を用いた。 (Example 2)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 1,800 and a molar ratio of ethylene oxide to propylene oxide of 40/60 was used. There was.
（実施例３）
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が２,３００、及び、エチレンオキシドとプロピレンオキシドのモル比が３０／７０である共重合ポリエーテルの１％水溶液を用いた。 (Example 3)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,300 and a molar ratio of ethylene oxide to propylene oxide of 30/70 was used. There was.
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が２,３００、及び、エチレンオキシドとプロピレンオキシドのモル比が３０／７０である共重合ポリエーテルの１％水溶液を用いた。 (Example 3)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,300 and a molar ratio of ethylene oxide to propylene oxide of 30/70 was used. There was.
（実施例４）
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が３,１００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Example 4)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 3,100 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が３,１００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Example 4)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 3,100 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
（実施例５）
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が１,１００、及び、エチレンオキシドとプロピレンオキシドのモル比が１０／９０である共重合ポリエーテルの１％水溶液を用いた。 (Example 5)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 1,100 and a molar ratio of ethylene oxide to propylene oxide of 10/90 was used. There was.
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が１,１００、及び、エチレンオキシドとプロピレンオキシドのモル比が１０／９０である共重合ポリエーテルの１％水溶液を用いた。 (Example 5)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 1,100 and a molar ratio of ethylene oxide to propylene oxide of 10/90 was used. There was.
（実施例６）
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が２,８００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Example 6)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,800 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が２,８００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Example 6)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,800 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
（実施例７）
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が２,５００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Example 7)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,500 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
ポリエーテルの種類以外は実施例１と同様にして実験を行い、重量平均分子量が２,５００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Example 7)
Experiments were carried out in the same manner as in Example 1 except for the type of polyether, and a 1% aqueous solution of a copolymerized polyether having a weight average molecular weight of 2,500 and a molar ratio of ethylene oxide to propylene oxide of 20/80 was used. There was.
（実施例８）
共重合ポリエーテルの１％水溶液を、１７５ｋｇ添加した以外は、実施例４と同様に行った。 (Example 8)
The procedure was the same as in Example 4 except that 175 kg of a 1% aqueous solution of the copolymerized polyether was added.
共重合ポリエーテルの１％水溶液を、１７５ｋｇ添加した以外は、実施例４と同様に行った。 (Example 8)
The procedure was the same as in Example 4 except that 175 kg of a 1% aqueous solution of the copolymerized polyether was added.
（実施例９）
共重合ポリエーテルの１％水溶液を、１,０５０ｋｇ添加した以外は、実施例４と同様に行った。 (Example 9)
The procedure was the same as in Example 4 except that 1,050 kg of a 1% aqueous solution of the copolymerized polyether was added.
共重合ポリエーテルの１％水溶液を、１,０５０ｋｇ添加した以外は、実施例４と同様に行った。 (Example 9)
The procedure was the same as in Example 4 except that 1,050 kg of a 1% aqueous solution of the copolymerized polyether was added.
（実施例１０）
重合率が４０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例４と同様に行った。 (Example 10)
When the polymerization rate reached 40%, the same procedure as in Example 4 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
重合率が４０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例４と同様に行った。 (Example 10)
When the polymerization rate reached 40%, the same procedure as in Example 4 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
（実施例１１）
重合率が８０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例４と同様に行った。 (Example 11)
When the polymerization rate reached 80%, the same procedure as in Example 4 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
重合率が８０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例４と同様に行った。 (Example 11)
When the polymerization rate reached 80%, the same procedure as in Example 4 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
（実施例１２）
共重合ポリエーテルの１％水溶液を、１７５ｋｇ添加した以外は、実施例２と同様に行った。 (Example 12)
The procedure was the same as in Example 2 except that 175 kg of a 1% aqueous solution of the copolymerized polyether was added.
共重合ポリエーテルの１％水溶液を、１７５ｋｇ添加した以外は、実施例２と同様に行った。 (Example 12)
The procedure was the same as in Example 2 except that 175 kg of a 1% aqueous solution of the copolymerized polyether was added.
（実施例１３）
重合率が４０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例２と同様に行った。 (Example 13)
When the polymerization rate reached 40%, the same procedure as in Example 2 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
重合率が４０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例２と同様に行った。 (Example 13)
When the polymerization rate reached 40%, the same procedure as in Example 2 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
（実施例１４）
重合率が８０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例２と同様に行った。 (Example 14)
When the polymerization rate reached 80%, the same procedure as in Example 2 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
重合率が８０％に到達した時点で、共重合ポリエーテルの１％水溶液を添加した以外は、実施例２と同様に行った。 (Example 14)
When the polymerization rate reached 80%, the same procedure as in Example 2 was carried out except that a 1% aqueous solution of the copolymerized polyether was added.
（比較例１）
還流コンデンサーを付しておらず、泡センサーを付した内容積１００ｍ3のステンレス製重合器を用いたこと、及び、ポリエーテル共重合体を用いていないこと以外は実施例１と同様にして行った。 (Comparative Example 1)
The procedure was the same as in Example 1 except that a stainless steel polymerizer having an internal volume of 100 m 3 equipped with a foam sensor was used without a reflux capacitor, and a polyether copolymer was not used. It was.
還流コンデンサーを付しておらず、泡センサーを付した内容積１００ｍ3のステンレス製重合器を用いたこと、及び、ポリエーテル共重合体を用いていないこと以外は実施例１と同様にして行った。 (Comparative Example 1)
The procedure was the same as in Example 1 except that a stainless steel polymerizer having an internal volume of 100 m 3 equipped with a foam sensor was used without a reflux capacitor, and a polyether copolymer was not used. It was.
（比較例２）
ポリエーテル共重合体を用いていないこと以外は実施例１と同様にして行った。 (Comparative Example 2)
The procedure was carried out in the same manner as in Example 1 except that the polyether copolymer was not used.
ポリエーテル共重合体を用いていないこと以外は実施例１と同様にして行った。 (Comparative Example 2)
The procedure was carried out in the same manner as in Example 1 except that the polyether copolymer was not used.
（比較例３）
以下のポリエーテル共重合体を使用した以外は実施例１と同様にして実験を行い、重量平均分子量が１５０万、及び、エチレンオキシドとプロピレンオキシドのモル比が８０／２０である共重合ポリエーテルの１％水溶液を用いた。 (Comparative Example 3)
Experiments were carried out in the same manner as in Example 1 except that the following polyether copolymer was used, and the copolymer polyether having a weight average molecular weight of 1.5 million and a molar ratio of ethylene oxide to propylene oxide of 80/20 was used. A 1% aqueous solution was used.
以下のポリエーテル共重合体を使用した以外は実施例１と同様にして実験を行い、重量平均分子量が１５０万、及び、エチレンオキシドとプロピレンオキシドのモル比が８０／２０である共重合ポリエーテルの１％水溶液を用いた。 (Comparative Example 3)
Experiments were carried out in the same manner as in Example 1 except that the following polyether copolymer was used, and the copolymer polyether having a weight average molecular weight of 1.5 million and a molar ratio of ethylene oxide to propylene oxide of 80/20 was used. A 1% aqueous solution was used.
（比較例４）
以下のポリエーテル共重合体を使用した以外は実施例１と同様にして実験を行い、重量平均分子量が１５,０００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Comparative Example 4)
Experiments were carried out in the same manner as in Example 1 except that the following polyether copolymer was used, and the copolymerized polyether having a weight average molecular weight of 15,000 and a molar ratio of ethylene oxide to propylene oxide of 20/80. A 1% aqueous solution of the above was used.
以下のポリエーテル共重合体を使用した以外は実施例１と同様にして実験を行い、重量平均分子量が１５,０００、及び、エチレンオキシドとプロピレンオキシドのモル比が２０／８０である共重合ポリエーテルの１％水溶液を用いた。 (Comparative Example 4)
Experiments were carried out in the same manner as in Example 1 except that the following polyether copolymer was used, and the copolymerized polyether having a weight average molecular weight of 15,000 and a molar ratio of ethylene oxide to propylene oxide of 20/80. A 1% aqueous solution of the above was used.
＜組成と評価結果＞
<Composition and evaluation results>
≪分散性の評価≫
共重合ポリエーテルの１％水溶液を調整し、該水溶液の粘度をデジタル回転粘度計ＤＶ３Ｔ（英弘精機株式会社製）によって測定した。なお、粘度の測定は２０℃で行い、粘度測定の回転数は実施例１～１０では２５０ｒｐｍ、比較例２では１００ｒｐｍで粘度測定を行った。共重合ポリエーテルの１％水溶液の粘度が１０ｃＰ以上を×、１．５ｃＰ以上１０ｃＰ未満を△、１．５ｃＰ未満を○とした。 ≪Evaluation of dispersibility≫
A 1% aqueous solution of the copolymerized polyether was prepared, and the viscosity of the aqueous solution was measured with a digital rotational viscometer DV3T (manufactured by Eiko Seiki Co., Ltd.). The viscosity was measured at 20 ° C., and the viscosity measurement was performed at 250 rpm in Examples 1 to 10 and 100 rpm in Comparative Example 2. The viscosity of the 1% aqueous solution of the copolymerized polyether was evaluated as x, 1.5 cP or more and less than 10 cP as Δ, and less than 1.5 cP as ◯.
共重合ポリエーテルの１％水溶液を調整し、該水溶液の粘度をデジタル回転粘度計ＤＶ３Ｔ（英弘精機株式会社製）によって測定した。なお、粘度の測定は２０℃で行い、粘度測定の回転数は実施例１～１０では２５０ｒｐｍ、比較例２では１００ｒｐｍで粘度測定を行った。共重合ポリエーテルの１％水溶液の粘度が１０ｃＰ以上を×、１．５ｃＰ以上１０ｃＰ未満を△、１．５ｃＰ未満を○とした。 ≪Evaluation of dispersibility≫
A 1% aqueous solution of the copolymerized polyether was prepared, and the viscosity of the aqueous solution was measured with a digital rotational viscometer DV3T (manufactured by Eiko Seiki Co., Ltd.). The viscosity was measured at 20 ° C., and the viscosity measurement was performed at 250 rpm in Examples 1 to 10 and 100 rpm in Comparative Example 2. The viscosity of the 1% aqueous solution of the copolymerized polyether was evaluated as x, 1.5 cP or more and less than 10 cP as Δ, and less than 1.5 cP as ◯.
≪壁面へのＰＶＣ付着の評価≫
重合缶壁面に付着した塩化ビニル樹脂付着量を評価した。１ｃｍ2当たりの塩化ビニル樹脂付着量が目視により１００粒以上を×、１０粒以上１００粒未満を△、１０粒未満を○とした。 ≪Evaluation of PVC adhesion to wall surface≫
The amount of vinyl chloride resin adhering to the wall surface of the polymerization can was evaluated. The amount of vinyl chloride resin adhered per 1 cm 2 was visually evaluated as x for 100 grains or more, Δ for 10 grains or more and less than 100 grains, and ○ for less than 10 grains.
重合缶壁面に付着した塩化ビニル樹脂付着量を評価した。１ｃｍ2当たりの塩化ビニル樹脂付着量が目視により１００粒以上を×、１０粒以上１００粒未満を△、１０粒未満を○とした。 ≪Evaluation of PVC adhesion to wall surface≫
The amount of vinyl chloride resin adhering to the wall surface of the polymerization can was evaluated. The amount of vinyl chloride resin adhered per 1 cm 2 was visually evaluated as x for 100 grains or more, Δ for 10 grains or more and less than 100 grains, and ○ for less than 10 grains.
≪１００ｍ3の重合缶での消泡効果の評価≫
添加なし（比較例２）でのレベルに対して、レベルの低下が１０ｃｍ未満を×、１０ｃｍ以上３０ｃｍ未満を△、３０ｃｍ以上５０ｃｍ未満を○、５０ｃｍ以上を◎とした。 ≪Evaluation of defoaming effect with 100m 3 polymerized can≫
With respect to the level without addition (Comparative Example 2), the decrease in level was marked as × for less than 10 cm, Δ for 10 cm or more and less than 30 cm, ○ for 30 cm or more and less than 50 cm, and ⊚ for 50 cm or more.
添加なし（比較例２）でのレベルに対して、レベルの低下が１０ｃｍ未満を×、１０ｃｍ以上３０ｃｍ未満を△、３０ｃｍ以上５０ｃｍ未満を○、５０ｃｍ以上を◎とした。 ≪Evaluation of defoaming effect with 100m 3 polymerized can≫
With respect to the level without addition (Comparative Example 2), the decrease in level was marked as × for less than 10 cm, Δ for 10 cm or more and less than 30 cm, ○ for 30 cm or more and less than 50 cm, and ⊚ for 50 cm or more.
≪可塑剤吸収量≫
内径２５ｍｍ、深さ８５ｍｍのアルミニウム合金製重合器の底にグラスファイバーを詰め、該重合器に試料ＰＶＣ１０ｇを投入し、次にジオクチルフタレート(ＤＯＰ)１５ｍｌを加えた。そして、３０分間放置して試料にＤＯＰを充分浸透させた後、１５００Ｇの加速度下で試料から過剰量のＤＯＰを遠心分離した。試料に吸収されたＤＯＰの量をＤＯＰ吸収前の試料の重量に対する重量％として求めた。 ≪Plasticizer absorption amount≫
Glass fiber was packed in the bottom of an aluminum alloy polymerizer having an inner diameter of 25 mm and a depth of 85 mm, 10 g of sample PVC was put into the polymerizer, and then 15 ml of dioctyl phthalate (DOP) was added. Then, after leaving it for 30 minutes to allow the sample to sufficiently permeate the DOP, an excess amount of DOP was centrifuged from the sample under an acceleration of 1500 G. The amount of DOP absorbed by the sample was determined as% by weight based on the weight of the sample before DOP absorption.
内径２５ｍｍ、深さ８５ｍｍのアルミニウム合金製重合器の底にグラスファイバーを詰め、該重合器に試料ＰＶＣ１０ｇを投入し、次にジオクチルフタレート(ＤＯＰ)１５ｍｌを加えた。そして、３０分間放置して試料にＤＯＰを充分浸透させた後、１５００Ｇの加速度下で試料から過剰量のＤＯＰを遠心分離した。試料に吸収されたＤＯＰの量をＤＯＰ吸収前の試料の重量に対する重量％として求めた。 ≪Plasticizer absorption amount≫
Glass fiber was packed in the bottom of an aluminum alloy polymerizer having an inner diameter of 25 mm and a depth of 85 mm, 10 g of sample PVC was put into the polymerizer, and then 15 ml of dioctyl phthalate (DOP) was added. Then, after leaving it for 30 minutes to allow the sample to sufficiently permeate the DOP, an excess amount of DOP was centrifuged from the sample under an acceleration of 1500 G. The amount of DOP absorbed by the sample was determined as% by weight based on the weight of the sample before DOP absorption.
≪嵩比重≫
ＪＩＳ Ｋ－６７２３に準じて試料ＰＶＣの嵩比重を測定した。 ≪Volume specific gravity≫
The bulk specific gravity of the sample PVC was measured according to JIS K-6723.
ＪＩＳ Ｋ－６７２３に準じて試料ＰＶＣの嵩比重を測定した。 ≪Volume specific gravity≫
The bulk specific gravity of the sample PVC was measured according to JIS K-6723.
Claims (4)
- 重合器を用いて、塩化ビニル単量体又は塩化ビニル単量体及びこれと共重合可能な単量体の混合物を水性媒体中で重合し、塩化ビニル系重合体を製造する方法であって、
前記重合器に、重量平均分子量が１０００～３５００及びエチレンオキシドとプロピレンオキシドのモル比が１０／９０～６０／４０である共重合ポリエーテルの水溶液を、前記共重合ポリエーテルとして、仕込んだ前記塩化ビニル単量体１００重量部に対して０.００５重量部～０.０５０重量部添加することを特徴とする、塩化ビニル系重合体の製造方法。 A method for producing a vinyl chloride-based polymer by polymerizing a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith in an aqueous medium using a polymerizer.
The vinyl chloride prepared by charging an aqueous solution of a copolymerized polyether having a weight average molecular weight of 1000 to 3500 and a molar ratio of ethylene oxide to propylene oxide of 10/90 to 60/40 into the polymerizer as the copolymerized polyether. A method for producing a vinyl chloride-based polymer, which comprises adding 0.005 parts by weight to 0.050 parts by weight with respect to 100 parts by weight of the monomer. - 前記重合において、重合率３０％～８０％の重合段階で前記共重合ポリエーテルの水溶液を添加することを特徴とする、請求項１に記載の塩化ビニル系重合体の製造方法。 The method for producing a vinyl chloride-based polymer according to claim 1, wherein in the polymerization, an aqueous solution of the copolymerized polyether is added at a polymerization step of a polymerization rate of 30% to 80%.
- 前記重合器の容量が容積５０ｍ3以上であることを特徴とする、請求項１又は２に記載の塩化ビニル系重合体の製造方法。 The method for producing a vinyl chloride-based polymer according to claim 1 or 2, wherein the capacity of the polymer is 50 m 3 or more.
- 前記重合器において、還流コンデンサーが付設されていることを特徴とする請求項１～３のいずれか１項に記載の塩化ビニル系重合体の製造方法。 The method for producing a vinyl chloride-based polymer according to any one of claims 1 to 3, wherein a reflux capacitor is attached to the polymer.
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| Application Number | Priority Date | Filing Date | Title |
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| MX2021015225A MX2021015225A (en) | 2019-06-19 | 2020-06-08 | Method for producing vinyl chloride polymer. |
| CN202080044218.0A CN113993911B (en) | 2019-06-19 | 2020-06-08 | Process for producing vinyl chloride polymer |
| EP20825871.5A EP3988584A4 (en) | 2019-06-19 | 2020-06-08 | Method for producing vinyl chloride polymer |
| US17/619,305 US20220403150A1 (en) | 2019-06-19 | 2020-06-08 | Method for producing vinyl chloride type polymer |
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| JP2019113439A JP7291550B2 (en) | 2019-06-19 | 2019-06-19 | Method for producing vinyl chloride polymer |
| JP2019-113439 | 2019-06-19 |
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| US (1) | US20220403150A1 (en) |
| EP (1) | EP3988584A4 (en) |
| JP (1) | JP7291550B2 (en) |
| CN (1) | CN113993911B (en) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53114891A (en) * | 1977-02-24 | 1978-10-06 | Mitsui Toatsu Chem Inc | Suspension polymerization of vinyl chloride |
| JPH0532707A (en) * | 1991-07-26 | 1993-02-09 | Sekisui Chem Co Ltd | Production of vinyl chrolide-based resin |
| JPH11322838A (en) * | 1998-05-19 | 1999-11-26 | Kanegafuchi Chem Ind Co Ltd | Production of vinyl chloride-based resin |
| JP2004238522A (en) * | 2003-02-06 | 2004-08-26 | Shin Etsu Chem Co Ltd | Preparation method of vinyl chloride polymer |
| JP2009062425A (en) * | 2007-09-05 | 2009-03-26 | Shin Dai-Ichi Vinyl Corp | Method for producing vinyl chloride-based polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02292310A (en) * | 1989-05-02 | 1990-12-03 | Shin Etsu Chem Co Ltd | Production of vinyl chloride polymer |
| JP4024491B2 (en) * | 2001-05-24 | 2007-12-19 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JP6627041B2 (en) * | 2017-08-02 | 2020-01-08 | サンノプコ株式会社 | Antifoaming agent for vinyl chloride resin slurry and method for producing vinyl chloride resin |
-
2019
- 2019-06-19 JP JP2019113439A patent/JP7291550B2/en active Active
-
2020
- 2020-06-08 WO PCT/JP2020/022522 patent/WO2020255776A1/en unknown
- 2020-06-08 EP EP20825871.5A patent/EP3988584A4/en active Pending
- 2020-06-08 CN CN202080044218.0A patent/CN113993911B/en active Active
- 2020-06-08 MX MX2021015225A patent/MX2021015225A/en unknown
- 2020-06-08 US US17/619,305 patent/US20220403150A1/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53114891A (en) * | 1977-02-24 | 1978-10-06 | Mitsui Toatsu Chem Inc | Suspension polymerization of vinyl chloride |
| JPH0532707A (en) * | 1991-07-26 | 1993-02-09 | Sekisui Chem Co Ltd | Production of vinyl chrolide-based resin |
| JPH11322838A (en) * | 1998-05-19 | 1999-11-26 | Kanegafuchi Chem Ind Co Ltd | Production of vinyl chloride-based resin |
| JP2004238522A (en) * | 2003-02-06 | 2004-08-26 | Shin Etsu Chem Co Ltd | Preparation method of vinyl chloride polymer |
| JP3996069B2 (en) | 2003-02-06 | 2007-10-24 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JP2009062425A (en) * | 2007-09-05 | 2009-03-26 | Shin Dai-Ichi Vinyl Corp | Method for producing vinyl chloride-based polymer |
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| JP2022133481A (en) | 2022-09-14 |
| JP7291550B2 (en) | 2023-06-15 |
| EP3988584A1 (en) | 2022-04-27 |
| EP3988584A4 (en) | 2023-06-28 |
| CN113993911A (en) | 2022-01-28 |
| CN113993911B (en) | 2023-09-08 |
| US20220403150A1 (en) | 2022-12-22 |
| MX2021015225A (en) | 2022-01-18 |
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